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Carroll rearrangement

About: Carroll rearrangement is a(n) research topic. Over the lifetime, 1483 publication(s) have been published within this topic receiving 23513 citation(s). more

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Journal ArticleDOI
01 Dec 1988-Chemical Reviews

435 citations

Journal ArticleDOI
TL;DR: Investigations demonstrate that the counterion of the azolium salt plays a key role in the formation of the catalytically active species in the synthesis of enantioenriched kojic acid derivatives. more

Abstract: In the presence of a chiral azolium salt (10 mol %), enols and ynals undergo a highly enantioselective annulation reaction to form enantiomerically enriched dihydropyranones via an N-heterocyclic carbene catalyzed variant of the Claisen rearrangement. Unlike other azolium-catalyzed reactions, this process requires no added base to generate the putative NHC-catalyst, and our investigations demonstrate that the counterion of the azolium salt plays a key role in the formation of the catalytically active species. Detailed kinetic studies eliminate a potential 1,4-addition as the mechanistic pathway; the observed rate law and activation parameters are consistent with a Claisen rearrangement as the rate-limiting step. This catalytic system was applied to the synthesis of enantioenriched kojic acid derivatives, a reaction of demonstrated synthetic utility for which other methods for catalytic enantioselective Claisen rearrangements have not provided a satisfactory solution. more

261 citations

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Topic's top 5 most impactful authors

Martin Hiersemann

12 papers, 479 citations

Krishna C. Majumdar

9 papers, 13 citations

Abdrakhmanov Ildus B

8 papers, 7 citations

Tolstikov Genrikh A

6 papers, 5 citations

Mark J. Kurth

5 papers, 127 citations